This application is a 371 of PCT/EP00/1196 filed Nov. 11, 2000.
The present invention relates to novel trifluoromethylpyrrolcarboxamides or trifluoromethylpyrrolethioamides which have microbicidal activity, in particular fungicidal activity. The invention also relates to the preparation of these substances, to agrochemical compositions which comprise at least one of the novel compounds as active ingredient, to the preparation of the compositions mentioned and to the use of the active ingredients or compositions in agriculture and horticulture for controlling or preventing infestation of plants by phytopathogenic microorganisms, preferably fungi.
The trifluoromethylpyrrolcarboxamides of the present invention have the general formula I 
wherein
X is oxygen or sulfur;
R1 is hydrogen, C1-C4alkyl unsubstituted or substituted, C1-C4alkoxy unsubstituted or substituted, or halogen;
R2 is C1-C4alkyl unsubstituted or substituted; and
A is orthosubstituted aryl; orthosubstituted heteroaryl; bicydoaryl unsubstituted or substituted; or bicycdoheteroaryl unsubstituted or substituted.
Surprisingly, it has now been found that the compounds of formula I exhibit improved biological properties which render them more suitable for the practical use in agriculture and horticulture.
Where asymmetrical carbon atoms are present in the compounds of formula I, these compounds are in optically active form. The invention relates to the pure isomers, such as enantiomers and diastereomers, as well as to all possible mites of isomers, e.g. mixtures of diastereomers, racemates or mixture of racemates.
Within the present specification alkyl denotes methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl and tert-butyl. Non-branched alkyl is preferred. Alkyl as part of other radicals such as alkoxy, haloakyl, alkylcycloalkyl, alkylcycloalkoxy, etc. is understood in an analogous way. Halogen will be understood generally as meaning fluoro, chloro, bromo or iodo. Fluoro, chloro or bromo are preferred meanings. Halogen as part of other radicals such as haloalkyl, habalkoxy, haloalkenyl, haloalkenyloxy, haloaryl or haloheteroaryl, etc. is understood in an analogous way. Haloaryl or haloheteroaryl designates mono to five times halo-substituted aryl, whereby the halogens are independently chosen. Where more than two halogens are present, the halogens are preferably the same, e.g. trifluorophenyl, trichlorophenyl, tetrachlorophenyl or perchlorophenyl.
Aryl is phenyl or naphthyl.
Heteroaryl will be understood as a 5- to 10membered ring that may contain up to 3 heteroatoms, such as nitrogen, oxygen or sulfur. The following list of examples is not exhaustive: furyl, thienyl, imidazolyl, pyrazolyl, thiazolyl, isothiazolyl, oxazolyl, isoxazolyl, oxadiazolyl, tniadiazblyl, triazol, tefazoly, pyrrolyl, dithiolyl, oxathio, dioxazolyl, oxathlazolyl, oxathlolyl, pyridyl, pyridazinyl, pyrimidinyl, pyrazinyl, tiazinyl, indolyl, benzoluranyl, beimkidazolyl, indazolyl, benzotazolyl, benzothiazolyl, benzoxazolyl, quinolinyl, isoquinolinyl, phthalazinyl, quinoxafinyl, quinazolinyl, cinnolinyl, naphthdinyl, isobebzofuranyl, isoindomy, benzothiadiazol, benotienyl, benzisoxazolyl, purinyl, 5,6-dihydro-1,4,2-dioxazinyl, and the like.
Bicydoaryl or bicycloheteroaryl will be understood as a 6-membered aryl or 6-membered heteroaryl, wherein it may contain up to 3 heteroatoms such as nitrogen, oxygen or sulfur, and which is fused to an additional ring. The fused ring may be aromatic, partially hydrogenated or completely saturated, may be a ring from 5 to 7 ring members, of which up to 3 memnbers may be heteroatoms selected from the group nitrogen, oxygen and sulfur. The following list of examples is not exhaustive: dihydroisobenzofuranyl, dihydroisoindolyl, and the like.
Preferred embodiments of compounds of the formula I are those wherein
X is oxygen or sulfur; or
X is oxygen; or
X is sulfur; or
R1 is hydrogen, C1-C4alkyl unsubstituted or substituted, C1-C4alkoxy unsubstituted or substituted, or halogen; or
R1 is hydrogen, C1-C4alkyl C1-C4haloalkyl, C1-C4alkoxy-C1-C4alkyl, C1-C4alkoxy,
C1-C4aloalkoxy, C1-C4haloalkoxy-C1-C4alkyl or halogen; or
R1 is hydrogen, C1-C4alkyl or C1-C4haloalkyl; or
R1 is hydrogen or C1-C3alkyl; or
R2 is C1-C4alkyl unsubstituted or substituted; or
R2 is C1-C4alkyl, C1-C4haloalkyl, C1-C4alkoxy-C1-C4alkyl, or C1-C4haloalkoxy-C1-C4alkyl; or
R2 is C1-C4alkyl, C1-C3haloalkyl; or C1-C3alkoxy-C1-C3alkyl; or
R2 is C1-C3alkyl or C1-C3alkoxy-C1-C3alkyl; or
A is orthosubstituted aryl; orthosubstituted heteroaryl; bicydoaryl unsubstituted or substituted; or bicycloheteroaryl unsubstituted or substituted; or
A is a group 
A is A1, A2, A3, A5, A8, A10, A13, A14, A17, A18, A20, A21, A22, A23, A24, A25, A26, A27, A29, A31or A32; or
A is A1, A2, A3, A17, A20, A21, A24, A25, A26, A27 or A31; or
R3 is C3-C7cycloalkyl unsubstituted or mono- to trisubstituted by halogen, hydroxy, C1-C4alkoxy, C1-C4haloalkyl, C2-C4alkenyl, C2-C4alkynyl, C1C4haloalkoxy or C1-C4alkyl; C4-C7cycloalkenyl unsubstituted or mono- to trisubstituted by halogen, hydroxy, C1-C4alkoxy, C1-C4haloakyl, C2-C4alkenyl, C2-C4alkynyl, C1C4haloalkoxy or C1-C4alkyl; C6-C7cyclodialkenyl unsubstituted or mono- to trisubstituted by halogen, hydroxy, C1-C4alkoxy, C1-C4haloalkyl, C2-C4alkenyl, C2-C4alkynyl, C1-C4haloalkoxy or C1-C4alkyl; thienyl, furyl, pyrrolyl pyrazolyl, oxazolyl, thiazolyl, isoxazolyl, isothiazolyl, tniadiazblyl, imidazolyl, tetrazolyl, tiazlnyl, benotienyl, 5,6dihydro-1,4,2-dioxazinyl, pyridyl, pyrazlnyl, pyridazinyl or pyrimidinyl, which are unsubstituted or substituted by halogen, C1-C4haloalkyl, C1-C8alkyl, hydroxy, cyano, nitro, CHO, C1-C4alkoxy-C1-C4alkyl, COOC1-C4alkyl, C1-C8haloalkoxy-C1-C4alkyl, C1-C8alkoxy or C1-C8haloalkoxy; or
R3 is C5-C7cycloalkyl unsubstituted or mono- to trisubstituted by halogen, hydroxy, C2-C4alkenyl, C2-C4alkynyl, C1-C3alkoxy or C1-C4alkyl; C5C7cycloalkenyl unsubstituted or mono- to trisubstituted by halogen, hydroxy, C1-C3alkoxy, C2-C4alkenyl, C2-C4alkynyl or C1-C4alkyl; C6-C7cyclodialkenyl unsubstituted or mono- to trisubstituted by halogen, hydroxy, C1-C3alkoxy, C2-C4alkenyl, C2-C4alkynyl or C1-C3alkyl; thienyl, furyl, oxazolyl, isoxazolyl, thiadiazolyl, triazinyl, pyridyl, pyrazinyl, pyridazinyl or pyrimidinyl, which are unsubstituted or substituted by halogen, C1-C4haloalkyl, C1-C4alkyl, hydroxy, C1-C4alkoxy or C1C4haloalkoxy; or
R3 is cyclohexyl, cyclohexenyl or cyclohexadienyl, which are unsubstituted or mono- to disubstituted by chloro, bromo, C1-C2alkyl C1-C2haloalkyl or C1-C2haloalkoxy, thienyl, furyl, triazinyl, pyridyl, pyrazinyl, pyridazinyl or pyrimidinyl which are unsubstituted or substituted by halogen, C1-C4alkyl, C1-C4haloalkyl or C1-C4haloalkoxy; or
R31 is C3-C7cycloalkyl, C3-C07cycloalkenyl or C5-C7cyloalkadienyl which are unsubstituted or substituted by halogen, C1-C6alkoxy, C1-C6alkoxy-C1-C6alkyl, C1-C6haloalkoxy-C1-C4alkyl, C1-C4alkyl, C1-C4haloalkyl, C1-C4haloalkoxy, C2-C4alkenyl or C2-C3alkynyl; phenyl unsubstituted or substituted by halogen, C1-C6 alkoxy, C1-C6aloalkoxy, C1-C4alkyl, C1-C4haloakyl, C2C4alkenyl, C2-C5alkynyl, CHO, COOC1-C4alkyl, C1-C4alkoxy, C1-C4alkyl, C1-C4alkyl-C1-C4alkoxy, C1-C4haloalkoxy-C1-C4alkyl, C1-C4haloalkyl-C1-C4alkoxy, cyano or nitro; thienyl, furyl, pyrrolyl, pyrazolyl, oxazolyl, thiazolyl, isoxazolyl, isothiazolyl, thiadiazolyl, imidazolyl, triazinyl, pyridyl, pyridazinyl, pyrazinyl or pyrimidinyl, which are unsubstituted or substituted by halogen, C1-C6haloalkyl, C1-C6alkyl, hydroxy, cyano, nitro, CHO, COOC1-C4alkyl, C1-C6haloalkoxy-C4-C4alkyl, C1C4alkoxy-C1-C4alkyl, C1-C6alkoxy or C1-C6haloalkoxy; or
R31 is C6-C7cycloalkyl, C6-C7cycloalkenyl or C6-C7cyloalkadienyl, which are unsubstituted or substituted by halogen, C1-C4alkyl, C1-C4alkoxy, C2-C4alkenyl, C2-C4alkynyl, C1-C4haloalkyl or C1-C4haloalkoxy, phenyl which is unsubstituted or substituted by halogen, C1-C4alkyl, C1-C4alkoxy, C1-C4haloalkyl or C1-C4haloalkoxy, thin, furyl, isoxazolyl, oxazoyl, thiadiazolyl, triazinyl, pyridyl, pyrimidinyl, pyrazinyl or pyridazinyl which are unsubstituted or substituted by halogen, C1-C4alkyl, C1-C4alkoxy, C1-C4haloalkyl or C1-C4haloalkoxy; or
R31 is cyclohexyl, cyclohexenyl or cyclohexadienyl, which are unsubstituted or substituted by halogen, C1-C4alkyl, C1-C4alkoxy, C1-C4haloalkyl or C1-C4haloalkoxy; thienyl, furyl, triazinyl, pyridyl, pyrazinyl, pyridazinyl or pyrimidinyl which are unsubstituted or substituted by halogen, C4-C4alkyl, C1-C4haloalkyl or C1-C4haloalkoxy; or
R1is hydrogen; cyano; nitro; halogen; C1-C4alkoxy; C1-C4haloalkyl; C1-C4alkyl; C1-C4alkoxy-C1-C4alkyl; C5-C7cycloalkyl unsubstituted or substituted by C1-C4alkyl or C1-C3haloalkyl; C1-C4haloalkoxy-C1-C4alkyl; or C1-C4haloalkoxy; or
R4 is hydrogen; halogen; C1-C4alkoxy; C1-C4alkyl; C5-C7cycloalkyl unsubstituted or substituted by C1-C3alkyl or C1-C3alkyl C1-C4haloalkyl; or C1-C4haloalkoxy, or
R4 is hydrogen; halogen; C1-C3alkoxy; C1-C3haloalkyl; C1-C3alkyl; C6-C7cycloalkyl, unsubstituted or substituted by C1-C3alkyl or C1-C3haloalkyl; or C1-C3haloalkoxy, or
R5, R6, R7, R8 and R9 are identical or different and are each independently of the others hydrogen, halogen, C1-C4haloalkyl, C1-C4alkyl, C1-C6haloalkoxy-C1-C4alkyl, C1-C4alkoxy, C1-C4haloalkoxy, C1-C4alkoxy-C1-C4alkyl or C3-C7cycloalkyl; or
R5, R6, R7 and R8 are identical or different and are each independently of the others hydrogen, C1-C4haloalkyl, C1-C4alkyl, C1-C4alkoxy or C1-C4haloalkoxy, or
R5, R6, R7 and R7 are identical or different and are each independently of the others hydrogen or C1-C3alkyl.
Within the group of compounds of formula I those compounds are preferred wherein:
R1 is hydrogen C1-C4alkyl, C1-C4haloalkyl, C1-C4alkoxy-C1-C4alkyl, C1-C4alkoxy, C1-C4haloalkoxy, C1-C4haloalkoxy-C1-C4alkyl or halogen;
R2 is C1-C4alkyl, C1-C4haloalkyl C1-C4alkoxy-C1-C4alkyl or C1-C4haloalkoxy-C1-C4alkyl;
A is a group 
and
R3 is C1-C4cycloalkyl unsubstituted or mono- to trisubstituted by halogen, hydroxy, C1-C4alkoxy, C1-C4haloalkyl, C2-C4alkynyl, C2-C4alkynyl, C1-C4haloalkoxy or C1-C4alkyl; C4-C7cycloalkenyl unsubstituted or mono- to trisubstituted by halogen, hydroxy, C1-C4alkoxy, C1-C4haloalkyl, C2-C4alkenyl, C2-C4alkynyl, C1-C4haloalkoxy or C1-C4alkyl; C6-C7cyclodialkenyl unsubstituted or mono- to trisubstituted by halogen, hydroxy, C1-C4alkoxy, C1-C4haloalkyl, C2-C4alkenyl, C2-C4alkynyl, C1-C4haloalkoxy or C1-C4alkyl; thienyl, furyl, pyrrolyl, pyrazolyl, oxazolyl, thiazolyl, isoxazolyl, isothiazolyl, thiadiazolyl, imidazolyl, tetrazolyl, triazinyl, benotienyl, 5,6dihydro-1,4,2-dioxazinyl, pyridyl, pyrazinyl, pyridazinyl or pyrimidinyl, which are unsubstituted or substituted by halogen, C1-C6haloalkyl, C1-C6alkyl, hydroxy, cyano, nitro, CHO, C1-C4alkoxy-C1-C4alkyl, COOC1-C4alkyl, C1-C6haloalkoxy-C1-C4alkyl, C1-C6alkoxy or C1-C6haloalkoxy;
R31 is C3-C7cycloalkyl, C3-C7cycloalkenyl or C5-C7cyloalkadienyl which are unsubstituted or substituted d by halogen, C1-C6alkoxy, C1-C6alkoxy-C1-C6alkyl, C1-C6haloalkoxy-C1-C4alkyl, C1-C4alkyl, C1-C4haloalkyl, C1-C4haloalkoxy, C2-C4alkenyl or C2-C5alkynyl; phenyl unsubstituted or substituted by halogen, C1-C6alkoxy, C1-C6haloalkoxy, C1-C4alkyl, C1-C4haloalkyl, C2-C4alkenyl, C2-C5alkynyl, CHO, COOC1-C4alkyl, C1-C4alkoxy-C1-C4alkyl, C1-C4alkyl-C1-C4alkoxy, C1-C4haloalkoxy-C1-C4alkyl, C1-C4haloalkyl, alkoxy, cyano or nitro; thienyl, furyl, pyrrolyl, pyrazolyl, oxazolyl, thiazolyl, isoxazolyl, isothiazolyl, thiadiazolyl, imidazolyl, triazinyl, pyridyl, pyridazinyl, pyrazinyl or pyrimidinyl, which are unsubstituted or substituted by halogen, C1-C6haloalkyl, C1-C6alkyl, hydroxy, cyano, nitro, CHO, COOC1-C4alkyl, C1-C6haloalkoxy-C1-C4alkyl, C1-C4alkoxy-C1-C4alkyl, C1-C6alkoxy or C1-C6haloalkoxy;
R4 is hydrogen; cyano; nitro; halogen; C1-C4alkoxy; C1-C4haloalkyl; C1-C4alkyl; C1-C4alkoxy-C1-C4alkyl; C5-C7unsubstituted or substituted by C1-C3alkyl or C1-CC3haloalkyl; C1-C4haloalkoxy-C1-C4alkyl: or C1-C4haloalkoxy; and
R5, R6, R7, R8 and R9 are identical or different and are each independently of the others hydrogen, halogen, C1-C4haloalkyl, C1-C4alkyl, C1-C6haloalkoxy-C1-C4alkyl, C1-C4alkoxy, C1-C4haloalkoxy, C1-C4alkoxy-C1-C4alkyl or C3-C7cycloalkyl (subgroup AA).
Cycloalkyl is, depending on the ring size, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl or cycloheptyl. Cycloalkenyl is, depending on the ring size, cyclopentyl, cyclohexenyl or cycloheptenyl. Cycloalkenyl is, depending on the ring size, cyclopentenyl, cyclohexenyl or cyclohexadienyl.
Alkenyl will be understood as meaning straight-chain or branched alkenyl such as alkyl, methallyl, 1-methylvinyl or but-2-en 1-yl. Preferred alkenyl radicals contain 3 to 4 carbon atoms in the chain.
Alkynyl can likewise, in accordance with the number of carbon atoms, be straight-chain or branched and is typically propargyl, but-1-yn1-yl or but-1-yn-3yl.
Within the group AA of compounds of formula I those compounds are preferred wherein X is oxygen (subgroup AB).
Another group of compounds of formula I within the group AA are those wherein X is sulfur (subgroup AC).
Within the subgroup AB are those compounds preferred wherein
R1 is hydrogen, C1-C4alkyl or C1-C4haloalkyl;
R2 is C1-C4alkyl, C1-C4haloalkyl or C1-C3alkoxy-C1-C3alkyl;
A is A1, A2, A3, A5, A8, A10, A13, A14, A17, A18, A20 A21, A22 A24, A25, A26,A27, A29, A31 or A32;
R3 is C5-C7cycloalkyl, unsubstituted or mono- to trisubstituted by halogen, hydroxy, C2-C4alkenyl C2-C4alkynyl, C1-C4alkyl or C1-C3alkoxy; C5-C7cycloalkenyl, unsubstituted or mono- to trisubstituted by halogen, hydroxy, C2-C4alkenyl, C2-C4alkynyl, C1-C3alkyl or C1-C3alkoxy; C5-C7cyclodialkenyl, unsubstituted or mono- to disubstituted by halogen, hydroxy, C2-C4alkenyl, C2-C4alkynyl, C1-C3alkyl or C1-C3alkoxy, thienyl, furyl, isoxazolyl, oxazoyl, thiadiazolyl, triazinyl, pyridyl, pyrimidinyl, pyrazinyl or pyridazinyl, which are unsubstituted or substituted by halogen, hydroxy, C1-C4alkyl, C1-C4haloalkyl, C1-C4alkoxy or C1-C1haloalkoxy;
R31 is C5-C7cycloalkyl, C5-C7cycloalkenyl or C5-C7, cyloalkadienyl, which are unsubstituted or substituted by halogen, C1-C4alkyl, C1-C4alkoxy, C2-C4alkenyl, C2-C4alkynyl, C1-C4haloalkyl or C1-C4haloalkoxy; phenyl which is unsubstituted or substituted by halogen, C1-C4alkyl, C1-C4alkoxy, C1-C4haloalkyl or C1-C4haloalkoxy; thienyl, furyl, isoxazolyl, oxazoyl, thiadiazolyl, triazinyl, pyridyl,pyrimidinyl, pyrazinyl or pyridazinyl which are unsubstituted or substituted by halogen, C1-C4alkyl, C1-C4alkoxy, C1-C4haloalkyl or C1C4haloalkoxy;
R4 is hydrogen; halogen; C1-C1alkyl; C1-C4alkoxy; C5-C7cycloalkyl unsubstituted or substituted by C1-C3alkyl or C1-C3haloalkyl; C1-C4haloalkyl; or C1-C4haloalkoxy; and
R5, R6, R7 and R8 are identical or different and are each independently of the others hydrogen, C1-C4alkyl, C1-C4alkoxy, C1-C4haloalkyl or C1-C4haloalkoxy (subgroup AB1).
Within the subgroup AB1 are those compounds more preferred wherein
A is A1, A2, A3, A17, A20, A21, A24, A25, A26, A27 or A31;
R1 is hydrogen or C1-C3alkyl;
R2 is C1-C4alkyl or C1-C4alkoxy-C1-C3alkyl;
R3 is cyclohexyl, cyclohexenyl or cyclohexadienyl, which are unsubstituted or mono- to disubstituted by chloro, bromo, C1-C2alkyl, C1-C2haloalkyl or C1-C2haloalkoxy; thienyl, furyl, triazinyl, pyridyl, pyrazinyl, pyridazinyl or pyrimidinyl which are unsubstituted or substituted by halogen, C1-C4alkyl, C1-C4haloalkyl or C1-C4haloalkoxy;
R31 is cyclohexyl, cyclohexenyl or cyclohexadienyl, which are unsubstituted or substituted by halogen, C1-C4alkyl C1-C4alkoxy, C1-C4haloalkyl or C1-C4haloalkoxy; thienyl, furyl, triazinyl, pyridyl, pyrazinyl, pyridazinyl or pyrimidinyl which are unsubstituted or substituted by halogen, C1-C4alkyl, C1-C4haloalkyl or C1-C4haloalkoxy;
R4 is hydrogen; halogen; C1-C3alkyl; C1-C3haloalkyl; C1-C3alkoxy; C5-C7cycloalkyl unsubstituted or substituted by C1-C3alkyl or C1-C3haloalkyl; or C1-C3haloalkoxy, and
R5, R6, R7 and R8 are identical or different and are each independently of the others hydrogen or C1-C3alkyl (subgroup AB2).
Within the subgroup AC are those compounds preferred wherein
R1 is hydrogen, C1-C4alkyl or C1-C4haloalkyl;
R2 is C1-C4alkyl, C1-C3haloalkyl or C1-C3alkoxy-C1-C3alkyl;
A is A1, A2, A3, A5, A8, A10, A13, A14, A17, A18, A20, A21, A22, A24, A25, A26, A27, A29, A31 or A32;
R3 is C5-C7cycloalkyl, unsubstituted or mono- to trisubstituted by halogen, hydroxy, C2-C4alkenyl, C2-C4alkynyl, C1-C3alkyl or C1-C3alkoxy; C5-C7cycloalkenyl, unsubstituted or mono to trisubstituted by halogen, hydroxy, C2-C4alkenyl, C2-C4alkynyl, C1-C3alkyl or C1-C3alkoxy;, C5-C7cyclodialkenyl, unsubstituted or mono- to disubstituted by halogen, hydroxy, C2-C4alkenyl, C2-C4alkynyl, C1-C3alkyl or C1-C3alkoxy; thienyl, furyl, isoxazolyl, oxazolyl, thiadiazolyl, triazinyl, pyridyl, pyrimidinyl, pyrazinyl or pyridazinyl, which are unsubstituted or substituted by halogen, hydroxy, C1-C4alkyl, C1-C4haloalkyl, C1-C4alkoxy or C1-C4haloalkoxy;
R31 is C5-C7cycloalkyl, C5-C7cycloalkenyl or C5-C7-cyloalkadienyl, which are unsubstituted or substituted by halogen, C1-C4a, C1-C4alkoxy, C2-C4alkenyl, C2-C4alkynyl, C1-C4haloalkyl or C1-C3haloalkoxy, phenyl which is unsubstituted or substituted by halogen, C1-C4alkyl, C1-C4alkoxy, C1-C4haloalkyl or C1-C4haloalkoxy; thienyl, furyl, isoxazolyl, oxazolyl, thiadiazolyl, triazinyl, pyridyl, pyrimidinyl, pyrazinyl or pyridazinyl which are unsubstituted or substituted by halogen, C1-C4alkyl, C1-C4alkoxy, C1-C4haloalkyl or C1-C4haloalkoxy,
R4 is hydrogen; halogen; C1C4alkyl; C1C4alkoxy; C5-C7haloalkyl; C7-C5cycloalkyl unsubstituted or substituted by C1-C3alkyl or C1-C3haloalkyl; or C1-C4haloalkoxy; and
R5, R6, R7 and R8 are identical or different and are each independently of the others hydrogen, C1-C4alkyl, C1-C4alkoxy, C1-C4haloalkyl or C1-C4-haloalkoxy (subgroup AC1).
Within the subgroup AC1 are those compounds more preferred wherein
A is A1, A2, A3, A17, A20, A21, A24, A25, A26, A27 or A31;
R1 is hydrogen or C1-C4alkyl;
R2 is C1-C3alkyl or C1-C3alkoxy-C1-C3alkyl;
R3 is cyclohexyl, cyclohexenyl or cyclohexadienyl, which are unsubstituted or mono- to disubstituted by chloro, bromo, C1-C2alkyl, C1-C2haloalkyl or C1-C2haloalkoxy; thienyl, furl, triazinyl, pyridyl, pyrazinyl, pyridazinyl or pyrimidinyl which are unsubstituted or substituted by halogen, C1-C4alkyl, C1-C4haloalkyl or C1-C4habalkoxy;
R31 is cyclohexyl, cyclohexenyl or cyclohexadienyl, which are unsubstituted or substituted by halogen, C1-C4alkyl, C1-C4alkoxy. C1-C4haloalkyl or C1-C4haloalkoxy; thienyl, furyl, triazinyl, pyridyl, pyrazinyl, pyridazinyl or pyrimidinyl which are unsubstituted or substituted by halogen, C1-C4alkyl, C1-C4haloalkyl or C1-C4haloalkoxy;
R4 is hydrogen; halogen; C1-C3-alkyl; C1-C3haloalkyl; C1-C4alkoxy; C5-C7cycloalkyl unsubstituted or substituted by C1-C3alkyl or C1-C3haloalkyl; or C1-C3haloalkoxy; and
R5, R6, R7 and R8 are identical or different and are each independently of the others hydrogen or C1-C3alkyl (subgroup AC2).
Within the subgroup AB are those compounds preferred wherein
A is A1 and
R3 is C5-C7cycloalkyl unsubstituted or monosubstituted by C1-C4alkyl or C1-C4haloalkyl (subgroup A83).
Preferred individual compounds are:
1methyl-4-trifloromethyl-1H-pyrrole-3caboxylic acid [1xe2x80x2-(3xe2x80x2-methylcyclohexyl)-2-benzamide];
1methyl-4-trifluoromethyl-1-H-pyrrole-3-carboxylic acid [1xe2x80x2-(3xe2x80x2-ethylcyclohexyl)-2-benzamide];
1methyl-4-trifluoromethyl-1H-pyrrole-3-caroxylic acid [1xe2x80x2-(3xe2x80x2-trifluoromethylcyclohexyl)-2-benzamide];
1methyl-4-trifluoromethyl-1H-pyrrole-3-carboxylic acid [1xe2x80x2-(3xe2x80x2-methylcyclohexyl)-2-benzamide];
1methyl-4 trifluoromethyl-1H-pyrrole-3-carboxylic acid [1xe2x80x2-(3xe2x80x2ethylcyclopentyl)-2-benzamide];
1methyl-4-trifluoromethyl-1H-pyrrole-3-carboxylic acid [1xe2x80x2-(3xe2x80x2-trifluoromethylcyclohexyl)-2-benzamide].
The compounds according to formula I may be prepared according to the following reaction schemes.
A) Synthesis of the pyrrole carboxylic acids:
Route 1 (Tosmic-route) 
Route 2 (Trifluoroacetoacetic acid-route, analogous to JP-07157466) 
B) Synthesis of the amides/thioamides 
B1) Synthesis of the amides wherein A is phenyl, pyridine or pyrimidine 
The xe2x80x9cin situxe2x80x9d prepared pyrazole carboxylic acid chloride reacts with an ortho-halosubstituted phenylamine in the presence of a solvent like toluene, benzene, xylene, hexane, cycolohexane, THF, chloroform or methylenechloride and in the presence of a base like sodium carbonate, sodium hydrogencarbonate, potassium carbonate, HOnig base, triethylamine or pyridine at a temperature between 0xc2x0 C. and reflux temperature. The obtained pyrazolecarboxamaide reacts with a boronic acid of the formula R3xe2x80x94B(OH)2 in the presence of a Pd-catalyst like Pd(P(pheny3)4, Pd(P(phenyl3))2Cl2, PdCl2dppb, Pd2(dba)3, Pd(OAc)2, PdOAc2/(o-tolyl)3P, Pd(OAc)2/dppf, Pd(PhCN)2Cl/Ph3As, Pd(CH3CN)2Cl2, Pd2(dba)3/P(tert.butyl)3, Pd(OAc)2/P(tert.butyl)2biphenyl, Pd(OAc)2/TPPTS, Pd(OAc)2/Py3, Pd(OAc)2/P(O-i-Pr)3, Pd(OAc)2/2-dimethylamino-2xe2x80x2-dicyclohextylphosphinobipheryl, Pd(OAc)2/2-dimethylamino2xe2x80x2-ditert.butylphosphinoblphenyl, Pd(OAc)2/(o-biphenyl)P(cyclohexyl)2 in a solvent like 1,2dimaehoxyethane/water, DMF, DMA, THF/water, dioxane/water, benzene, toluene, xylene and others and a base like sodium carbonate, sodium hydrogencarbonate, potassium carbonate, cesium carbonate, potassium phosphate, triethylamine, sodium hydroxide, sodium ethylate, sodium tert.butylate, silver oxide, barium carbonate, potassium fluoride or cesium fluoride at a temperature between 0xc2x0 C. and reflux temperature.
C) Synthesis of the ortho-substituted amines Axe2x80x94NH2:
The compounds are either known from the literature or can be prepared by known methods. For example the following amines or important intermediates for the synthesis of the amines can be prepared according to the following literature:
A1xe2x80x94NH2: Tetrahedron 1993,49,49-64 or EP-83975 or J.Org.Chem. 1995,60,292;
A2xe2x80x94NH2: EP-737682;
A3xe2x80x94NH2: J.Chem.Res.(S) 1978,11,11428 or Chem.Scr.1972,2,245;
A13xe2x80x94NH2: Org.Prep.Procedures Int. 1989,21, 141;
A21xe2x80x94NH2: J.Chem.Soc.Perkin I 1981,5,1591;
A25xe2x80x94NH2: Tetrahedron 1993,49,4964 or Heterocycles 1999,51,721;
A26xe2x80x94NH2: Synthesis 1996,10,1015 or Synthesis 1994,9,931;
A27xe2x80x94NH2: Liebigs Ann.Chemie 1977,537-544 or J.Med.Chem. 1975,18,623;
A31xe2x80x94NH2: EP-315502;
A32xe2x80x94NH2: J.Pesticide Science 1993,18,245;
A30xe2x80x94NH2: J.Heterocyclic Chem. 1982,19,1285,
Surprisingly, it has now been found that the novel compounds of formula I have, for practical purposes, a very advantageous spectrum of activities for protecting plants against diseases that are caused by fungi as well as by bacteria and viruses.
The compounds of formula I can be used in the agricultural sector and related fields of use as active ingredients for controlling plant pests. The novel compounds are distinguished by excellent activity at low rates of application, by being well tolerated by plants and by being environmentally safe. They have very useful curative, preventive and systemic properties and are used for protecting numerous cultivated plants. The compounds of formula I can be used to inhibit or destroy the pests that occur on plants or parts of plants (fruit, blossoms, leaves, stems, tubers, roots) of different crops of useful plants, while at the same time protecting also those parts of the pants that grow later e.g. from phytopathogenic microorganisms.
It is also possible to use compounds of formula I as dressing agents for the treatment of plant propagation material, in particular of seeds (fruit, tubers, grains) and plant cuttings (e.g. rice), for the protection against fungal infections as well as against phytopathogenic fungi occurring in the soil.
The compounds I are, for example, effective against the phytopathogenic fungi of the following classes: Fungi imperfecti (e.g. Botrylis, Pyricularia, Helminthosporium, Fusarium, Septoria, Cercospora and Alternaria) and Basidiomycetes (e.g. Rhizoctonia, Hemileia, Puccinia). Additionally, they are also effective against the Ascomycetes classes (e.g. Venturia and Erysiphe, Podosphaera, Monilinla, Uncinula) and of the Oomycetes classes (e.g. Phylophthora, Pylhium, Plasropara). Outstanding activity has been observed against powdery mildew (Eysiphe spp.). Furthermore, the novel compounds of formula I are effective against phytopathogenic bacteria and viruses (e.g. against Xanthononas spp, Pseudomonas spp, Erwinia amylovora as well as against the tobacco mosaic virus).
Within he scope of present invention, target crops to be protected typically comprise the following species of plants: cereal (wheat, barley, rye, oat, rice, maize, sorghum and rebate species); beet (sugar beet and fodder beet); pomes, drupas and soft fruit (apples, pears, plums, peaches, almonds, cherries, strawberries, raspberries and blackberries); leguminous plants (beans, lentil, peas, soybeans); oil plants (rape, mustard, poppy, olives, sunflowers, coconut, castor oil plants, cocoa beans, groundnuts); cucumber plants (pumpkins, cucumbers, melons); fibre plants (cotton, flax, hemp, jute); citrus fruit (oranges, lemons, grapefruit, mandarins); vegetables (spinach, lettuce, asparagus, cabbages, carrots, onions, tomatoes, potatoes, paprika); lauraceae (avocado, cinnamomum, camphor) or plants such as tobacco, nuts, coffee, eggplants, sugar cane, tea, pepper, vines, hops, bananas and natural rubber plants, as well as ornamental.
The compounds of formula I are used in unmodified form or, preferably, together with the adjuvants conventionally employed in the art of formulation. To this end they are conveniently formulated in known manner to emulsifiable concentrates, coatable pastes, directly sprayable or dilutable solutions, dilute emulsions, wettable powders, soluble powders, dusts, granulates, and also encapsulations e.g. in polymeric substances. As with the type of the compositions, the methods of application, such as spraying, atomising, dusting, scattering, coating or pouring, are chosen in accordance with the intended objectives and the prevailing circumstances. The compositions may also contain further adjuvants such as stabilisers, antifoams, viscosity regulators, binders or tackifiers as well as fertillisers, micronutrient donors or other formulations for obtaining special effects.
Suitable carriers and adjuvants can be solid or liquid and are substances useful in formulation technology, e.g. natural or regenerated mineral substances, solvents, dispersants, wettirg agents, tackifiers, thickeners, binders or fertilisers. Such carriers are for example described in WO 97/33890.
The compounds of formula I are normally used in the form of compositions and can be applied to the crop area or plant to be treated, simultaneously or in succession with further compounds. These further compounds can be e.g. fertilisers or micronutrient donors or other preparations which influence the growth of plants. They can also be selective herbicides as well as insecticides, fungicides, bactericides, nematicides, molluscides or mixtures of several of these preparations, if desired together with further carriers, surfactants or application promoting adjuvants customarily employed in the art of formulation.
The compounds of formula I can be mixed with other fungicides, resulting in some cases in unexpected synergistic activities.
Mixing components which are particularly preferred are azoles such as azaconazole, bitertanol, propiconazole, difenoconazole, diniconazole, cyproconazole, epoxiconazole, fluquinconazole, flusiazole, flutriafol, hexaconazole, imazalil, imibenconazole, ipconazole, tebuoonazole, tetraconazole, fenbuconazole, metconazole, myclobutanil, perfurazoate, penconazole, bromuconazole, pyrifnox, prochloraz, triadimefon, triadlmenol, triffumizole or triticonazole; pyrimidinyl carbinoles such as ancymidol, fenarimol or nuarimol; 2-amino-pyrimidine such as bupirimate, dimethirimol or ethirimol; morpholines such as dodemorph, fenpropidin, fenpropimorph, spiroxanin or tridemorph; anilinopyrimdines such as cyprodinil, pyrimethanil or mepanipyrim; pyrroles such as fenpiclonil or fludioxonil; phenylamides such as benalaxyl, furalaxyl, metalaxyl, R-metalaxyl, ofurace or oxadixyl; benzimidazoles such as benomyl, carbendazim, debacarb, fuberidazole or thiabendazole; dicarboximides such as chlozolinate, dichlozoline, iprdine, myclozoline, procymidone or vinclozolin; carboxamides such as carboxin, fenfuram, flutolanil, mepronil, oxycarboxin or thifluzamide; guanidines such as guazatne, dodine or iminoctadine; strobilurines such as azoxystrobin, kresoxim-methyl, metominostrobin, SSF-129, methyl 2-[(2-trifluoromethyl)pyrid-yloxymethyl]-3methoxycacrylate or 2-[xcex1{[(xcex1-methyl-3-trifluoromethyl-benzyl)imino]oxy}-o-toly]glyoxylic acid-methylester-O-methyloxime (trifloxystrobin); dithiocarbamates such as ferbam, mancozeb, maneb, metiram, propineb, thiram, zineb or ziram; N-halomethylthio-dicarboximides such as captafol, captan, dichlofluanid, fluorormide, folpet or tolfluanid; copper compounds such as Bordeaux mixture, copper hydroxide, copper oxychloride, copper sulfate, cuprous oxide, mancopper or oxine-copper, nitrophenol derivatives such as dinocap or nitrothal-isopropyl; organo phosphorous derivatives such as edifenphos, iprobenphos, isoprothiolane, phosdiphen, pyrazophos or toclofos-methyl; and other compounds of diverse structures such as aciberolar-S-methyl, anilazine, blasticidin-S, chinomethionat, chloroneb, chlorothalonil, cymoxanil, dichlone, dicomezine, dicloran, diethofencarb, dimethomorph, dithianon, etridiazole, famoxadone, fenamidone, fentin, ferimzone, fluazinam, flusuffamide, fenhexamid, fosetyl-alurinium, hymexazol, kasugamycin, methasuifocarb, pencycuron, phthalide, polyoxins, probenazole, propamocarb, pyroquilon, quinoxyfen, quintozene, sulfur, triazoxide, tricyclazole, triforine, validamycin, (S)-5-methyl-2-methylthio-5-phenyl-3-phenyl-amino3,5-dihydroimidazol-4-one (RPA 407213), 3,5-dichloro-N-(3chlro-1-ethyl-1-methyl-2-oxopropyl)4-methylbenzamide (RH7281), N-alkyl-4,5-dimethyl-2-timethylsilythiophene-3-carboxamide (MON 65500), 4-chloro-4-cyano-N,N-dimethyl-5-p-tolylimidazole-1-sulfon-amide (IKF-916), N-(1-cyano-1,2-dimethylpropyl)-2-(2,4dichlorophenoxyy)-propionamide (AC 382042), or iprovalicarb (SZX 722).
A preferred method of applying a compound of formula I, or an agrochemical composition which contains at least one of said compounds, is follar application. The frequency of application and the rate of application will depend on the risk of infestation by the corresponding pathogen. However, the compounds of formula I can also penetrate the plant through the roots via the soil (systemic action) by drenching the locus of the plant with a liquid formulation, or by applying the compounds in solid form to the soil, e.g. in granular form (soil application). In crops of water rice such granulates can be applied to the flooded rice field. The compounds of formula I may also be applied to seeds (coating) by impregnating the seeds or tubers either with a liquid formulation of the fungicide or coating them with a solid formulation.
The formulation, i.e. the compositions containing the compound of formula I and, if desired, a solid or liquid adjuvant, are prepared in known manner, typically by intimately mixing and/or grinding the compound with extenders, e.g. solvents, solid carriers and, optionally, surface active compounds (surfactants).
The agrochemical formulations will usually contain from 0.1 to 99% by weight, preferably from 0.1 to 96% by weight of the compound of formula I, 99.9 to 1% by weight preferably 99.8 to 5% by weight, of a solid or liquid adjuvant, and from 0 to 25% by weight, preferably from 0.1 to 25% by weight, of a surfactant.
Advantageous rates of application are normally from 5 g to 2 kg of active ingredient (a.i.) per hectare (ha), preferably from 10 g to 1 kg a.i/ha, most preferably from 20 g to 600 g a.i/ha. When used as seed drenching agent, convenient dosages are from 10 mg to 1 g of active substance per kg of seeds.
Whereas it is preferred to formulate commercial products as concentrates, the end user will normally use dilute formulations.
The following non-limiting examples illustrate the above-described invention in more detail. Temperatures are given in degrees Celsius. The following abbreviations are used: m.p.=melting point; b.p.=boiling point xe2x80x9cNMRxe2x80x9d means nuclear magnetic resonance spectrum. MS stands for mass spectrum. xe2x80x9c%xe2x80x9d is percent by weight, unless corresponding concentrations are indicated in other units.